CN109047788A - A kind of ultrafine yttria Doped Tungsten composite nanometre powder preparation method of cyclic oxidation reduction - Google Patents
A kind of ultrafine yttria Doped Tungsten composite nanometre powder preparation method of cyclic oxidation reduction Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The present invention proposes a kind of ultrafine yttria Doped Tungsten composite nanometre powder preparation method of cyclic oxidation reduction, ball milling after tungsten oxide powder and yttrium nitrate or yttrium oxide powder are mixed；Ultra-fine W-Y is obtained with hydrogen reducing2O3Powder；Then its reoxidized is obtained into WOx‑Y2O3Powder restores to obtain W-Y with two step of hydrogen2O3Powder, oxidation and reduction process are repeated as many times；Again by W-Y2O3Powder ball milling；Finally W-Y is removed with hydrogen2O3The oxide layer on powder surface finally obtains superfine nano W-Y2O3Composite nanometre powder.The ultrafine yttria Doped Tungsten composite nanometre powder preparation method of cyclic oxidation reduction is smaller than powder grain made from traditional mechanical alloying method, it is small to reunite, average grain size can reach 30nm or less, and crystallite size distributed pole is narrow, oxygen content can be down to 1.41%, and the method has significant advantage.
Description
Technical field
The invention proposes a kind of ultrafine yttria Doped Tungsten W-Y2O3The technology of preparing of composite nanometre powder, belongs to powder
Preparation engineering technical field.
Background technique
Tungsten and its alloy have many excellent performances, high-melting-point, high heat conductance, high density, low thermal coefficient of expansion, excellent
Corrosion resistance etc., be widely used in the fields such as aerospace, electronics, chemical industry.In fusion nuclear energy field, W can be applied to high temperature, strong
Flow the extreme Service Environment such as ion irradiation and stable state hot-fluid, it is considered to be most promising the first wall protection towards plasma
Material.
But W has black brittleness, and interface binding power is small, recrystallization temperature is low and the characteristics such as irradiation hardening and embrittlement, tungsten
Application be restricted, also be always limit its nuclear fusion field application problem.At present effective method be the second phase more
Dissipate reinforcing and refined crystalline strengthening.On the one hand, Y2O3It is optimal oxide dispersion intensifying phase, it can significantly refine W crystal grain, W crystal grain
Smaller, oxide Second Phase Particle is uniform in the transgranular distribution more disperse of tungsten, and the performance of tungsten alloy is more excellent, on meeting
State more stringent military service demand in each application field；On the other hand, refined crystalline strengthening is uniquely to improve the strength of materials and hardness
While, and the intensifying method of material plasticity and toughness is improved, and superfines is sintered to us to obtain crystal grain tiny, fine and close
It spends high grained material and provides possibility.
Superfine nano powder is generally referred to as diameter in 100nm powder below, has high sintering activity.Powder is got over
Carefully, sintering activity is higher, and sintering temperature can be substantially reduced in follow-up sintering, shortens soaking time, so crystal grains fine, densification
Degree improves.
Compound W-Y is obtained at present2O3The main method of superfine nano powder have mechanical attrition method, but traditional ball milling side
Method has many deficiencies: (1) as Ball-milling Time is elongated, the effect for refining crystal grain is more unobvious, in Preparation and
Sintering of nanometer W-2 wt.%Y2O3 composite powders(JOURNAL OF RARE EARTHS,
Vol.33, No.7, July 2015, P.752) in a text it can be seen that crystal grain is decreased to be difficult to continue to refine after 50nm, and with
Ball-milling Time increase the impurity introduced also the more；(2) although W and Y2O3Abundant ball milling, but be mainly particle between two-phase
Between contact, oxide Second Phase Particle is seldom distributed in transgranular when follow-up sintering, is mainly distributed on grain boundaries and easy segregation
It grows up, hence it is evident that deteriorate tungsten-bast alloy mechanical property；(3) although powder is relatively thin after ball milling but surface-active for traditional ball grinding method
It is very high, layer of oxide layer can be formed on surface, significantly improve oxygen content, deteriorate sintering character and tungsten-bast alloy mechanical property.
Therefore, expect that powder is thinner, particle is smaller, and the lower composite nanometre powder of oxygen content improves traditional machinery
Ball-milling method preparation process is most important.The invention proposes a kind of ultrafine yttria Doped Tungsten composite Nanos of cyclic oxidation reduction
The preparation method of powder.
Summary of the invention
In view of the deficiencies of the prior art, the invention proposes a kind of ultrafine yttria Doped Tungsten of cyclic oxidation reduction is compound
The preparation method of nanometer powder.The average grain size for the composite powder that the technology enables to reaches 30nm hereinafter, crystal grain
Superfine and size distribution is extremely narrow, and oxygen content can be as small as 1.41%.
Specific technical solution is as follows:
1. a kind of preparation method of the ultrafine yttria Doped Tungsten composite nanometre powder of cyclic oxidation reduction, including following step
It is rapid:
(1) by tungsten oxide WO3Ball mill ball milling is used after powder and yttrium oxide or the mixing of yttrium nitrate powder；
(2) composite powder after ball milling is obtained into ultra-fine W-Y with hydrogen in furnace2O3Composite nanometre powder；
(3) W-Y for then obtaining step (2)2O3Composite nanometre powder carries out oxidation-reduction process in furnace, in air
Oxidation obtains WO in atmospherex-Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with pure two step of hydrogen2O3Composite Nano
Powder；
(4) step (3) oxidation and reduction process are repeated 1~6 time, obtains the smaller ultra-fine W-Y of crystal grain, particle2O3It is compound
Nanometer powder；
(5) again by W-Y2O3Composite nanometre powder ball mill is in argon atmosphere with revolving speed for 300~400r/min ball milling
2~5h obtains the smaller powder of particle；
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, in atmosphere of hydrogen, temperature be 700~
800 DEG C of 0.5~1h of heat preservation remove W-Y2O3The tungsten oxide on composite nanometre powder surface, and it is cooling in atmosphere of hydrogen, it is final to obtain
The ultra-fine W-Y of low oxygen content2O3Composite nanometre powder.
Yttrium oxide or yttrium nitrate account for tungsten oxide WO in the step (1)30.40%~1.59%.
Step (1) ball mill is with revolving speed for 200~400r/min ball milling 6~for 24 hours.
The step (2) is with hydrogen in 700~900 DEG C of 1.5~3h of reduction.
Oxidizing temperature and time are respectively as follows: 350~500 DEG C in the step (3), 0.33~1h；Two step reduction temperatures and
Time is respectively as follows: 550~650 DEG C, 1~2h, 700~800 DEG C, 1~2h.
Oxidation and reduction process repeat 2~3 times in the step (4).
Above-mentioned steps (1) (2) are when ball milling reaches the refinement limit, then use H2Reduction, WO3Become W, W crystal grain ratio WO3Crystal grain
It is smaller, that is, breach the attainable grain size limit of ball milling institute；Yttrium nitrate in this way, decomposing during subsequent heat becomes
Y2O3, crystal grain also becomes smaller；WO3There is fraction that can depend on yttrium oxide forming core when reduction, yttrium oxide is coated, yttrium oxide is distributed in crystalline substance
Interior ratio improves.With 0.4wt%Y2O3WO3-Y2O3For composite nanometre powder, the scanned picture of ball milling 12h such as Fig. 1 is brilliant
Grain average grain diameter is 90.1nm, is 0.5wt%Y after hydrogen reducing2O3W-Y2O3Composite nanometre powder, scanned picture such as Fig. 2,
Crystal grain average grain diameter is 55.4nm, and after this illustrates ball milling 12h, composite powder crystal grain is more coarse and size distribution is very uneven,
Composite powder obviously attenuates after hydrogen reducing.
Above-mentioned steps (3) (4) are the processes of cyclic oxidation reduction, and redox number is more, and crystal grain, particle are thinner, but
Number is more, and required cost is also more, comprehensively considers redox totally 3~4 suboptimum.Cyclic oxidation reduction principle: when W powder quilt
It is oxidized to WOXWhen, due to WOXVolume is big compared with W powder product, and this solid phase transformation will cause biggish internal stress, causes WOX?
The fragmentation of grain, particle reduce and become uniformly, and this loosening body structure is more conducive to subsequent hydrogen reduction and obtains more fine powder；In oxygen
WO during changeXBlue tungsten oxide WO including significant proportion2.9, blue tungsten WO2.9Make tungsten source ratio WO3Have great advantage, WO2.9Than
WO3The prominent advantages such as chemical activity height, large specific surface area, rate of reduction are fast and powder size is easily controllable, therefore also contribute to
Obtain superfine nano powder.With 0.5wt%Y2O3W-Y2O3For composite powder, redox 3 times, scanned picture such as Fig. 3,
Crystal grain average grain diameter is 40.4nm, and compared with Fig. 2, front technique is identical, but Fig. 3 has carried out the mistake of 3 cyclic oxidations reduction more
Journey, apparent refinement occurs for crystal grain and particle diameter distribution is more uniform.
Above-mentioned steps (5) are ultra-fine W-Y after broken cyclic oxidation reduction2O3The bulky grain of composite nanometre powder, makes powder
Degree of scatter increases, and particle sphericity improves.
Above-mentioned steps (6) are one and remove ultra-fine W-Y2O3The process of W surface oxide layer in composite nanometre powder, because receiving
Rice flour end is thinner, and surface-active is bigger, and surface has layer of oxide layer, will affect the mechanics of subsequent sintering character and tungsten alloy
Performance, therefore final step is answered to reduce the content of oxygen in atmosphere of hydrogen.With 0.5wt%Y2O3W-Y2O3For composite powder,
It is 3.10% without step (6) oxygen content after cyclic oxidation reduction, carrying out step (6) oxygen content is 1.41%, is contained by oxygen
The comparative illustration of amount leads to the necessity that hydrogen removes surface oxidation tungsten again after ball milling.
Advantages of the present invention:
1, compared with traditional Mechanical Alloying, composite nano oxide WO3-Y2O3Reduction can break ball milling
The limitation of particle size obtains more tiny powder.
2, by cyclic oxidation restore, powder grain size can be made to reach 30nm hereinafter, to the size of crystal grain, shape,
Accurate regulation is realized in distribution.
3, composite oxides WO3-Y2O3Cyclic oxidation reduction powder grain obtained is small and size distribution is extremely narrow, subsequent burning
Junction temperature can reduce, and sintering time can also shorten.
4, the present invention is not only able to achieve the preparation of superfine nano powder, while being also very suitable for that single batch is a large amount of compound to be received
The preparation of rice flour end.
Detailed description of the invention
Fig. 1: WO3-Y2O3WO after composite oxides ball milling3-Y2O3SEM picture；
Fig. 2: WO3-Y2O3W-Y after composite oxides reduction2O3SEM picture；
Fig. 3: W-Y2O3W-Y after redox 3 times2O3SEM picture；
Fig. 4: W-Y2O3W-Y after oxido-reductase 14 time2O3SEM picture；
Fig. 5: W-Y2O3W-Y after redox 7 times2O3SEM picture.
Specific embodiment
Feature of the invention is further described below by example, but the invention is not limited to following examples.
Embodiment 1
(1) by 100g tungsten oxide WO3With planetary ball after powder and 0.4g yttrium oxide powder (yttrium oxide accounts for 0.4%) mixing
Grinding machine is with revolving speed for 300r/min ball milling 12h.
(2) by the composite nano oxide powder after ball milling in hydrogen gas stream 800 DEG C of reductase 12 h, obtain W-Y2O3It is compound
Nanometer powder.
(3) then by W-Y2O3Composite nanometre powder reoxidized in air atmosphere (500 DEG C of heat preservation 0.33h) obtains
WOx-Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with two step of hydrogen2O3Composite nanometre powder (600 DEG C of heat preservation 1.5h,
800 DEG C of heat preservation 1.5h).
(4) oxidation and reduction process are repeated 3 times.
(5) W-Y after again restoring cyclic oxidation2O3Composite nanometre powder planetary ball mill in argon atmosphere with
Revolving speed is 300r/min ball milling 4h.
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, and temperature is stopped in atmosphere of hydrogen for 800 DEG C
0.5h is stayed, and cooling in atmosphere of hydrogen, finally obtains 0.5%Y2O3Ultra-fine W-Y2O3Composite nanometre powder.
The preparation method of tungsten composite powder is adulterated by the ultrafine yttria that cyclic oxidation restores, it is flat that we have obtained crystal grain
The ultra-fine W-Y that partial size is 31.6nm, oxygen content is 1.41%2O3Composite nanometre powder, scanned picture such as Fig. 4, average crystal grain ruler
Very little reduction and size distribution narrow, and wherein tungsten ingredient is α-W by material phase analysis.This illustrates the method for cyclic oxidation reduction
And crystallite size narrowly distributing smaller than powder average grain size made from traditional mechanical alloying method, oxygen content is low, more traditional
Mechanical alloy method the method has significant advantage.
Embodiment 2
(1) by 100g tungsten oxide WO3With planetary after powder and 0.8g yttrium oxide powder (yttrium oxide accounts for 0.79%) mixing
Ball mill is with revolving speed for 400r/min ball milling 6h.
(2) by the composite nano oxide powder after ball milling in hydrogen gas stream 700 DEG C of reduction 3h, obtain W-Y2O3It is compound
Nanometer powder.
(3) then by W-Y2O3Composite nanometre powder reoxidized in air atmosphere (350 DEG C of heat preservation 1h) obtains WOx-
Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with two step of hydrogen2O3Composite nanometre powder (550 DEG C of heat preservation 2h, 800 DEG C
Keep the temperature 1h).
(4) oxidation and reduction process are repeated 6 times.
(5) W-Y after again restoring cyclic oxidation2O3Composite nanometre powder planetary ball mill in argon atmosphere with
Revolving speed is 400r/min ball milling 3h.
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, and temperature is stopped in atmosphere of hydrogen for 750 DEG C
0.67h is stayed, and cooling in atmosphere of hydrogen, finally obtains 1%Y2O3Ultra-fine W-Y2O3Composite nanometre powder.
The preparation method of tungsten composite powder is adulterated by the ultrafine yttria that cyclic oxidation restores, it is flat that we have obtained crystal grain
The ultra-fine W-Y that partial size is 28.6nm, oxygen content is 1.67%2O3Composite nanometre powder, scanned picture such as Fig. 5, average crystal grain ruler
Very little reduction and size distribution narrow, and wherein tungsten ingredient is α-W by material phase analysis.This illustrates the method for cyclic oxidation reduction
And crystallite size narrowly distributing smaller than powder average grain size made from traditional mechanical alloying method, oxygen content is low, more traditional
Mechanical alloy method the method has significant advantage.
Embodiment 3
(1) by 100g tungsten oxide WO3With planetary after powder and 1.62g yttrium oxide powder (yttrium oxide accounts for 1.59%) mixing
Ball mill with revolving speed be 200r/min ball milling for 24 hours.
(2) by the composite nano oxide powder after ball milling in hydrogen gas stream 900 DEG C of reduction 1.5h, obtain W-Y2O3It is multiple
Close nanometer powder.
(3) then by W-Y2O3Composite nanometre powder reoxidized in air atmosphere (450 DEG C of heat preservation 0.67h) obtains
WOx-Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with two step of hydrogen2O3Composite nanometre powder (650 DEG C of heat preservation 1h, 700
DEG C heat preservation 2h).
(4) oxidation and reduction process are repeated 1 times.
(5) W-Y after again restoring cyclic oxidation2O3Composite nanometre powder planetary ball mill in argon atmosphere with
Revolving speed is 300r/min ball milling 4h.
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, and temperature is stopped in atmosphere of hydrogen for 700 DEG C
1h is stayed, and cooling in atmosphere of hydrogen, finally obtains 2%Y2O3Ultra-fine W-Y2O3Composite nanometre powder.
The preparation method of tungsten composite powder is adulterated by the ultrafine yttria that cyclic oxidation restores, it is flat that we have obtained crystal grain
The ultra-fine W-Y that partial size is 34.6nm, oxygen content is 1.99%2O3Composite nanometre powder, average grain size reduces and granularity point
Cloth narrows, and wherein tungsten ingredient is α-W by material phase analysis.This illustrates that the method for cyclic oxidation reduction is closed than traditional machinery
Powder average grain size made from aurification method is small and crystallite size narrowly distributing, and oxygen content is low, compared with tradition machinery alloy approach this
Method has significant advantage.
Embodiment 4
(1) by 100g tungsten oxide WO3With planetary after powder and 0.97g yttrium nitrate powder (yttrium nitrate accounts for 0.96%) mixing
Ball mill is with revolving speed for 300r/min ball milling 12h.
(2) by the composite oxide power after ball milling in hydrogen gas stream 800 DEG C of reductase 12 h, obtain W-Y2O3Composite Nano
Powder.
(3) then by W-Y2O3Composite nanometre powder reoxidized in air atmosphere (450 DEG C of heat preservation 0.5h) obtains WOx-
Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with two step of hydrogen2O3Composite nanometre powder (650 DEG C of heat preservation 1h, 750 DEG C
Keep the temperature 1.8h).
(4) oxidation and reduction process are repeated 2 times.
(5) W-Y after again restoring cyclic oxidation2O3Composite nanometre powder planetary ball mill in argon atmosphere with
Revolving speed is 300r/min ball milling 4h.
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, and temperature is stopped in atmosphere of hydrogen for 750 DEG C
0.5h is stayed, and cooling in atmosphere of hydrogen, finally obtains 0.5%Y2O3Ultra-fine W-Y2O3Composite nanometre powder.
The preparation method of tungsten composite powder is adulterated by the ultrafine yttria that cyclic oxidation restores, it is flat that we have obtained crystal grain
The ultra-fine W-Y that partial size is 26.6nm, oxygen content is 1.66%2O3Composite nanometre powder, average grain size reduces and granularity point
Cloth narrows, and wherein tungsten ingredient is α-W by material phase analysis.This illustrates that the method for cyclic oxidation reduction is closed than traditional machinery
Powder average grain size made from aurification method is small and crystallite size narrowly distributing, and oxygen content is low, compared with tradition machinery alloy approach this
Method has significant advantage.
Embodiment 5
(1) by 100g tungsten oxide WO3With planetary after powder and 0.97g yttrium nitrate powder (yttrium nitrate accounts for 0.96%) mixing
Ball mill is with revolving speed for 300r/min ball milling 10h.
(2) by the composite oxide power after ball milling in hydrogen gas stream 800 DEG C of reduction 1.5h, obtain W-Y2O3It is compound to receive
Rice flour end.
(3) then by W-Y2O3Composite nanometre powder reoxidized in air atmosphere (500 DEG C of heat preservation 0.5h) obtains WOx-
Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with two step of hydrogen2O3Composite nanometre powder (600 DEG C of heat preservation 1.5h, 750
DEG C heat preservation 1.5h).
(4) oxidation and reduction process are repeated 5 times.
(5) W-Y after again restoring cyclic oxidation2O3Composite nanometre powder planetary ball mill in argon atmosphere with
Revolving speed is 300r/min ball milling 4h.
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, and temperature is stopped in atmosphere of hydrogen for 750 DEG C
0.5h is stayed, and cooling in atmosphere of hydrogen, finally obtains 0.5%Y2O3Ultra-fine W-Y2O3Composite nanometre powder.
The preparation method of tungsten composite powder is adulterated by the ultrafine yttria that cyclic oxidation restores, it is flat that we have obtained crystal grain
The ultra-fine W-Y that partial size is 29.6nm, oxygen content is 1.86%2O3Composite nanometre powder, average grain size reduces and granularity point
Cloth narrows, and wherein tungsten ingredient is α-W by material phase analysis.This illustrates that the method for cyclic oxidation reduction is closed than traditional machinery
Powder average grain size made from aurification method is small and crystallite size narrowly distributing, and oxygen content is low, compared with tradition machinery alloy approach this
Method has significant advantage.
Claims (6)
1. a kind of preparation method of the ultrafine yttria Doped Tungsten composite nanometre powder of cyclic oxidation reduction, comprising the following steps:
(1) by tungsten oxide WO3Ball mill ball milling is used after powder and yttrium oxide or the mixing of yttrium nitrate powder；
(2) composite powder after ball milling is obtained into ultra-fine W-Y with hydrogen in furnace2O3Composite nanometre powder；
(3) W-Y for then obtaining step (2)2O3Composite nanometre powder carries out oxidation-reduction process in furnace, in air atmosphere
Middle oxidation obtains WOx-Y2O3Composite nanometre powder, then restore to obtain ultra-fine W-Y with pure two step of hydrogen2O3Composite nano powder
End；
(4) step (3) oxidation and reduction process are repeated 1~6 time, obtains the smaller ultra-fine W-Y of crystal grain, particle2O3Composite Nano
Powder；
(5) again by W-Y2O3Composite nanometre powder ball mill in argon atmosphere with revolving speed be 300~400r/min ball milling 2~
5h obtains the smaller powder of particle；
(6) finally by the W-Y after ball milling2O3Composite nanometre powder is placed in furnace, and in atmosphere of hydrogen, temperature is 700~800 DEG C
0.5~1h of heat preservation removes W-Y2O3The tungsten oxide on composite nanometre powder surface, and it is cooling in atmosphere of hydrogen, finally obtain hypoxemia
The ultra-fine W-Y of content2O3Composite nanometre powder.
2. the method as described in claim 1, it is characterized in that yttrium oxide or yttrium nitrate account for tungsten oxide WO in the step (1)3's
0.40%~1.59%.
3. the method as described in claim 1, it is characterized in that the step (1) ball mill is with revolving speed for 200~400r/min ball
Mill 6~for 24 hours.
4. the method as described in claim 1, it is characterized in that the step (2) is with hydrogen in 700~900 DEG C of 1.5~3h of reduction.
5. the method as described in claim 1, it is characterized in that in the step (3) oxidizing temperature and time be respectively as follows: 350~
500 DEG C, 0.33~1h；Two step reduction temperatures and time are respectively as follows: 550~650 DEG C, 1~2h, 700~800 DEG C, 1~2h.
6. the method as described in claim 1, it is characterized in that oxidation and reduction process repeat 2~3 times in the step (4).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894626A (en) * | 2019-03-22 | 2019-06-18 | 天津大学 | A kind of rotary calcining of Yttrium oxide doping tungsten composite powder and reducing preparation method |
| CN115383121A (en) * | 2022-08-24 | 2022-11-25 | 北京工业大学 | Method for controlling refining degree of rare earth composite refractory metal powder based on midway cyclic crushing |
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